U.S. patent application number 16/084314 was filed with the patent office on 2019-03-28 for process for controlling the malodor "sweat", using bacterial spores capable of inhibiting or preventing the production of such malodor.
This patent application is currently assigned to Henkel AG & Co. KGaA. The applicant listed for this patent is Henkel AG & Co. KGaA. Invention is credited to Michael Kandzia, Rainer Simmering, Mirko Weide.
Application Number | 20190093049 16/084314 |
Document ID | / |
Family ID | 55527449 |
Filed Date | 2019-03-28 |
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United States Patent
Application |
20190093049 |
Kind Code |
A1 |
Kandzia; Michael ; et
al. |
March 28, 2019 |
PROCESS FOR CONTROLLING THE MALODOR "SWEAT", USING BACTERIAL SPORES
CAPABLE OF INHIBITING OR PREVENTING THE PRODUCTION OF SUCH
MALODOR
Abstract
The present disclosure generally relates to a method for
degrading laundry malodor "sweat" preferably with regard to the
treatment of hard and/or soft surfaces, and more particularly
relates to the degradation of the laundry malodor "sweat" in the
context of a textile treatment method using bacterial spores.
Inventors: |
Kandzia; Michael; (Solingen,
DE) ; Simmering; Rainer; (Grevenbroich, DE) ;
Weide; Mirko; (Duesseldorf, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Henkel AG & Co. KGaA |
Duesseldorf |
|
DE |
|
|
Assignee: |
Henkel AG & Co. KGaA
Duesseldorf
DE
|
Family ID: |
55527449 |
Appl. No.: |
16/084314 |
Filed: |
March 10, 2017 |
PCT Filed: |
March 10, 2017 |
PCT NO: |
PCT/EP2017/055632 |
371 Date: |
September 12, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/381 20130101;
C11D 11/0023 20130101; A61L 9/013 20130101; D06F 35/008 20130101;
C11D 11/0017 20130101; C11D 3/0068 20130101 |
International
Class: |
C11D 3/00 20060101
C11D003/00; C11D 3/38 20060101 C11D003/38; C11D 11/00 20060101
C11D011/00; D06F 35/00 20060101 D06F035/00; A61L 9/013 20060101
A61L009/013 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 14, 2016 |
EP |
16160054.9 |
Claims
1. A method of inhibiting or preventing the production of laundry
malodor "sweat", comprising contacting a fabric or a laundry
washing machine with bacterial spores of at least one species of
Bacillus, which is selected from the group of Bacillus
amyloliquefaciens, Bacillus tequilensis, Bacillus subtilis,
Bacillus atrophaeus, Bacillus vallismortis, Bacillus mojavensis,
and combinations thereof.
2. The method according to claim 1, wherein the method comprises
contacting the fabric or the laundry washing machine with
combinations of bacterial spores of one or more of the species of
claim 1.
3. The method according to claim 1, wherein the laundry malodor is
caused by Alphaproteobacteria.
4. A use of bacterial spores comprising using bacterial spores of
at least one species of Bacillus selected from the group of
Bacillus amyloliquefaciens, Bacillus tequilensis, Bacillus
subtilis, Bacillus atrophaeus, Bacillus vallismortis, Bacillus
mojavensis, and combinations thereof, for inhibiting or preventing
the production of the laundry malodor "sweat".
5. A use of bacterial spores comprising using bacterial spores of
at least one species of Bacillus, which is selected from the group
of Bacillus amyloliquefaciens, Bacillus tequilensis, Bacillus
subtilis, Bacillus atrophaeus, Bacillus vallismortis, Bacillus
mojavensis, and combinations thereof, in washing or cleaning
agents, fabric softeners, hygienic rinsers or post wash additives
for inhibiting or preventing the production of the laundry malodor
"sweat".
6. The method of claim 1 further comprising: combining the
bacterial spores with a detergent prior to contacting the fabric or
laundry washing machine with the bacterial spores.
7. The method of claim 1 further comprising: combining the
bacterial spores with a fabric softener prior to contacting the
fabric or laundry washing machine with the bacterial spores.
8. The method of claim 1 further comprising: combining the
bacterial spores with a hygienic rinser prior to contacting the
fabric or laundry washing machine with the bacterial spores.
9. The method of claim 1 further comprising: combining the
bacterial spores with a post wash additive prior to contacting the
fabric or laundry washing machine with the bacterial spores.
10. The use of claim 4 further comprising: using two or more of the
spores of the species of Bacillus selected from the group of
Bacillus amyloliquefaciens, Bacillus tequilensis, Bacillus
subtilis, Bacillus atrophaeus, Bacillus vallismortis and/or
Bacillus mojavensis.
11. The use of claim 4 further comprising: combining the spores
with a detergent.
12. The use of claim 11 further comprising: washing laundry with
the detergent and the spores.
13. The use of claim 5 further comprising: combining the bacterial
spores with the washing or cleaning agents, fabric softeners,
hygienic rinsers or post wash additives prior to inhibiting or
preventing the production of the laundry malodor.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a U.S. National-Stage entry under 35
U.S.C. .sctn. 371 based on International Application No
PCT/EP2017/055632, filed Mar. 10, 2017 which was published under
PCT Article 21(2) and which claims priority to European Application
No. 16160054.9, filed Mar. 14, 2016, which are all hereby
incorporated in their entirety by reference.
TECHNICAL FIELD
[0002] The present disclosure generally relates to a method for
degrading malodors preferably with regard to the treatment of hard
and/or soft surfaces, and more particularly relates to the
degradation of malodors in the context of a textile treatment
method.
BACKGROUND
[0003] Malodor is a growing problem, particularly in laundry, with
the changed habits of lower temperature washing, front load wash
machines that save water but leave behind residual water between
loads allowing bacterial biofilms to flourish, line drying clothes
to save energy rather than appliance drying, and the increased
popularity of manmade fabrics, such as athletic wear, that appear
to retain odors more than natural fabrics.
[0004] An important consumer requirement, which also plays a role
e.g. in the utilization of washing, cleaning, or care-providing
agents, therefore includes in the elimination or at least
diminution of malodors (i.e. off-odors) or undesired odors.
Off-odors derive from specific olfactorily active compounds that
are also referred to as "malodorants." Malodorants are
foul-smelling compounds having so-called kakosmophoric groups, e.g.
amine derivatives and sulfur derivatives. The presence of such
off-odors generally results in a negative effect on human comfort,
and for that reason the consumer makes an effort to extinguish
these odors. Often, however, the off-odors are not extinguished but
merely masked. It is usual to use for this purpose products that
contain volatile, usually pleasant-smelling substances, and that
even in small quantities can mask foul odors.
[0005] These solutions, however, are not completely effective as
they are short-term. There is a need in the art for new solutions
for controling the problem of malodor.
[0006] It is therefore the object of the present disclosure to
provide the consumer with a further capability for bringing about
an inhibition, degradation or prevention of malodors.
BRIEF SUMMARY
[0007] Methods and uses of bacterial spores for controlling malodor
are provided. In an exemplary embodiment, a method includes
inhibiting or preventing laundry malodor by contacting a fabric or
a laundry washing machine with bacterial spores. The bacterial
spores are at least one species of Bacillus, and are selected from
the group of Bacillus amyloliquefaciens, Bacillus tequilensis,
Bacillus subtilis, Bacillus atrophaeus, Bacillus vallismortis,
Bacillus mojavensis, and combinations thereof.
[0008] A use of a bacterial spore is provided in another
embodiment. The use includes inhibiting or preventing laundry
malodor with at least one species of Bacillus. The at least one
species of Bacillus is selected from the group of Bacillus
amyloliquefaciens, Bacillus tequilensis, Bacillus subtilis,
Bacillus atrophaeus, Bacillus vallismortis, Bacillus mojavensis,
and combinations thereof.
[0009] A use of bacterial spores is provided in yet another
embodiment. The use includes inhibiting or preventing laundry
malodor with bacterial spores in washing or cleaning agents, fabric
softeners, hygienic rinsers, or post wash additives. The bacterial
spores are selected from the group of Bacillus amyloliquefaciens,
Bacillus tequilensis, Bacillus subtilis, Bacillus atrophaeus,
Bacillus vallismortis, Bacillus mojavensis, and combinations
thereof.
DETAILED DESCRIPTION
[0010] The following detailed description is merely exemplary in
nature and is not intended to limit the disclosure or the
application and uses of the subject matter as described herein.
Furthermore, there is no intention to be bound by any theory
presented in the preceding background or the following detailed
description.
[0011] The present disclosure provides a method of inhibiting or
preventing the production of the laundry malodor "sweat",
comprising contacting a fabric or a laundry washing machine with
bacterial spores of at least one species of Bacillus, which is
selected from the group including Bacillus amyloliquefaciens,
Bacillus tequilensis, Bacillus subtilis, Bacillus atrophaeus,
Bacillus vallismortis and/or Bacillus mojavensis.
[0012] The Bacillus species mentioned above or mixtures of those
are commercially available as Freshen Herbal.RTM. and Drain Ease
Open.RTM. from Novozymes A/S, Denmark, and UBFE Kultur.RTM. and WC
Kultur.RTM. from Julius Hoesch GmbH & Co. KG, 52353
Duren-Hoven, Germany.
[0013] The contacting can occur before, during, or after the
washing process. Fabrics preferably are contacted with the
bacterial spores during the washing process; washing machines may
alternatively or additionally be contacted with the bacterial
spores in between two washing processes.
[0014] Combinations of bacterial spores of such species and/or
isolates may also be used, such as blends of two or more species
and/or isolates, three or more species and/or isolates, etc.
Preferred are combinations comprising spores of Bacillus subtilis
and Bacillus mojavensis. Also preferred are combinations comprising
spores of Bacillus subtilis and Bacillus atrophaeus and/or Bacillus
vallismortis.
[0015] The present disclosure also provides the use of said
bacterial spores in inhibiting the malodor "sweat", in particular
in washing or cleaning agents, fabric softeners, hygienic rinsers
or post wash additives.
[0016] The methods and compositions of the present disclosure may
be used to treat an existing odor problem and/or as a preventative
treatment to prevent a potential odor problem. The present
disclosure may be used, for example, to inhibit malodor in laundry
washing machines/processes, dry cleaning machines/processes, steam
cleaning machines/processes, carpet cleaning machines/processes,
dish washing machines/processes, and other cleaning
machines/processes.
[0017] Malodor may be generated from a number of sources, mostly
microbial and in particular bacterial sources (including compounds
derived or produced therefrom). Sources of malodor causing
bacteria, include bacterium species selected from the group
including of Bacillus amyloliquefaciens, Acinetobacter junii,
Bacillus subtilis, Janibacter melois, Sphingobium ummariense,
Sphingomonas panni, Sphingomonadaceae, Actinobacter tandoii,
Junibacter melonis, Curtobacterium flaccumfaciens subsp.
flaccumfaciens, Flavobacterium denitrificans, Staphylococcus
epidermidis, Escherichia coli, Leclercia adecarboxylata,
Enterobacter sp., Cronobacter sakazakii, Bacillus megaterium,
Sphingobacterium faecium, Enterobacter cloacae, Pseudomonas
veronii, Microbacterium luteolum, Morganella morganii, Bacillus
cereus, Pseudomonas sp., Pseudomonas-marginalis, Citrobacter sp.,
Escherichia coli strain JCLys5, Roseomonas aquatic, Pseudomonas
panipatensis, Brevibacillus subtilis subtilis, Micrococcus luteus,
Bacillus pumilus, Ralstonia eutropha, Caulobacter fusiformis,
Stenotrophomonas maltophilia, Rhodococcus opacus, Breviundimonas
intermedia, Agrobacterium tumefaciens and in particular
Alphaproteobacteria (a class of bacteria in the phylum
Proteobacteria), and/or a combination thereof, and/or substances
derived therefrom.
[0018] The methods and compositions may also be applied directly to
an article treated (e.g., cleaned) in the cleaning machine or
cleaning process, such as, to a laundry treated in the machine. The
article may be treated before cleaning, during the cleaning
process, after the cleaning processes and any combination thereof.
Examples of such articles to be treated include laundry, carpets,
and fabrics.
[0019] The term "fabrics" encompasses all kind of fabrics,
textiles, fibers, clothes garments, and fabrics used on, e.g.,
furniture and cars. The term "laundry" refers to already used
and/or stained/soiled clothes in need of washing, and is in
contrast to newly manufactured fabrics. Washing laundry may be
carried out in private households and in commercial and
institutional facilities, such as, hospitals, prisons, uniform
service companies. Washing of newly manufactured fabrics is mainly
done in the textile industry. The fabric or laundry may be made
from any suitable material. In preferred embodiments the fabrics
and/or laundry are made from cellulosic materials, synthetic
materials and/or man-made fibers, or blends thereof. Examples of
contemplated cellulosic materials include cotton, viscose, rayon,
ramie, linen, lyocell (e.g., TENCEL.TM., produced by Courtaulds
Fibers), or blends thereof, or blends of any of these fibers
together with synthetic or man-made fibers (e.g., polyester,
polyamid, nylon) or other natural fibers such as wool and silk,
such as viscose/cotton blends, lyocell/cotton blends, viscose/wool
blends, lyocell/wool blends, cotton/wool blends; flax (linen),
ramie and other fabrics and/or laundry based on cellulose fibers,
including all blends of cellulosic fibers with other fibers such as
wool, polyamide, acrylic and polyester fibers, e.g.,
viscose/cotton/polyester blends, wool/cotton/polyester blends,
flax/cotton blends etc. The fabric and/or laundry may also be a
synthetic materials, e.g., including essentially 100% polyester,
polyamid, nylon, respectively. The term "wool," means any
commercially useful animal hair product, for example, wool from
sheep, camel, rabbit, goat, llama, and known as merino wool,
Shetland wool, cashmere wool, alpaca wool, mohair etc. and includes
wool fibers and animal hair. The method of the present disclosure
can be used on wool or animal hair material in the form of top,
fiber, yarn, or woven or knitted fabrics.
[0020] The treating may include contacting the odor-generating
organism(s) or odor-generating compound(s) present in the cleaning
machine or cleaning process with the bacterial spores. Such
contacting may include contacting a surface of a machine with the
bacterial spores and/or contacting a process water or cleaning
composition used in the cleaning machine with the bacterial
spores.
[0021] Contacting means contacting the odor-causing organism and/or
odor causing compound with the bacterial spores.
[0022] The ability to prepare spores and vegetative cells is
considered routine in the art. See Tzeng, Y. M., Y. K. Rao, et al.
(2008). "Effect of cultivation conditions on spore production from
Bacillus amyloliquefaciens B128 and its antagonism to Botrytis
elliptica." Journal of Applied Microbiology 104(5): 1275-1282.
[0023] Compositions of the present disclosure comprise bacterial
spores as described herein. The bacterial spores should be present
in effective amounts. The terms "effective amount", "effective
concentration" or "effective dosage" are defined herein as the
amount, concentration or dosage of odor-controling bacterial spores
that can inhibit the malodor caused by the odor causing organism or
substances derived therefrom on articles, articles subjected to a
cleaning machine or cleaning process, and/or cleaning machines. The
actual effective dosage in absolute numbers depends on factors
including: the odor causing organisms(s) in question; whether the
aim is prevention or reduction of malodor; other ingredients
present in the composition, and also the articles and/or cleaning
machine in question.
[0024] In an embodiment an effective dosage of the bacterial spores
as described herein would be introduced to the detergent at a final
concentration of about 1.times.10.sup.2-1.times.10.sup.9 CFU/g of
detergent, with a preferred range of about
1.times.10.sup.3-1.times.10.sup.7 CFU/g of detergent.
[0025] In another embodiment an effective dosage of the bacterial
spores as described herein would be introduced to a fabric softener
or hygienic rinser or at a final concentration of about
1.times.10.sup.1-1.times.10.sup.9 CFU/g of the fabric softener or
hygienic rinser, with a preferred range of about
1.times.10.sup.2-1.times.10.sup.7 CFU/g of the fabric softener or
hygienic rinser.
[0026] In yet another embodiment an effective dosage of the
bacterial spores as described herein would be introduced to a post
wash additive at a final concentration of about
1.times.10.sup.1-1.times.10.sup.9 CFU/g of the post wash additive,
with a preferred range of about 1.times.10.sup.1-1.times.10.sup.6
CFU/g of the post wash additive.
[0027] Effective amounts can be determined by one skilled in the
art using routine assays.
[0028] The bacterial spores of the present disclosure can be used
in combination with or as an ingredient of a washing product, such
as detergents and/or fabric softeners in particular, including but
not limited to aerosols, powders, solids, creams, etc., for use,
e.g., in cleaning machines, cleaning processes and/or articles
treated in cleaning machines or cleaning processes, such as,
fabrics.
[0029] The compositions of the present disclosure may in an
embodiment have a pH in the range of from about 5 to about 10 and
may further include water and/or one or more preservatives. For
preservation of compositions comprising bacterial spores of
Bacillus amyloliquefaciens, for example, the following
preservatives can be useful:
chloromethylisothiazolinone/methylisothiazolinone (CMIT/MIT)
(Kathon.RTM. or others); MIT (Neolone.RTM. or others);
1,2-benzisothiazolin-3-one (BIT) (if allowed in personal care);
CMIT/MIT+EDTA; CMIT/MIT+Biodegradable Chelator; MIT+EDTA;
MIT+Biodegradable Chelator; BIT+EDTA; BIT+Biodegradable Chelator;
Bronopol; 2-Phenoxyethanol; 2-Phenoxyethanol+Biodegradable
Chelator; Potassium sorbate (used at low pH); Sodium benzoate (used
at low pH); Salt; Glycerol; Propylene Glycol; Essential Oils;
Dichlorobenzyl alcohol; Triclosan.RTM.; Parabens; and
1-Phenoxy-2-propanol and 2-Phenoxy-1-propanol. In an embodiment,
the preservative is 2-Phenoxyethanol;
2-Phenoxyethanol+Biodegradable Chelator; Potassium Sorbate (used at
low pH); Sodium Benzoate (used at low pH); Salt; Glycerol;
Propylene Glycol; or one of more Essential Oils--e.g., white
mustard seed, tea tree, rosewood, or some citrus oils. In another
embodiment, the preservative is 2-Phenoxyethanol;
2-Phenoxyethanol+Biodegradable Chelator; or Glycerol. Accordingly,
an embodiment of the present disclosure is directed to a
composition comprising bacterial spores as described herein and a
preservative selected from the group including
chloromethylisothiazolinone/methylisothiazolinone (CMIT/MIT)
(Kathon.RTM. or others); MIT (Neolone.RTM. or others);
1,2-benzisothiazolin-3-one (BIT) (if allowed in personal care);
CMIT/MIT+EDTA; CMIT/MIT+Biodegradable Chelator; MIT+EDTA;
MIT+Biodegradable Chelator; BIT+EDTA; BIT+Biodegradable Chelator;
Bronopol; 2-Phenoxyethanol; 2-Phenoxyethanol+Biodegradable
Chelator; Potassium sorbate (used at low pH); Sodium benzoate (used
at low pH); Salt; Glycerol; Propylene Glycol; Essential Oils;
Dichlorobenzyl alcohol; Triclosan.RTM.; Parabens; and
1-Phenoxy-2-propanol and 2-Phenoxy-1-propanol. In an embodiment,
the preservative is 2-Phenoxyethanol;
2-Phenoxyethanol+Biodegradable Chelator; Potassium Sorbate (used at
low pH); Sodium Benzoate (used at low pH); Salt; Glycerol;
Propylene Glycol; or one of more Essential Oils--e.g., white
mustard seed, tea tree, rosewood, or some citrus oils,
2-Phenoxyethanol; 2-Phenoxyethanol+Biodegradable Chelator; or
Glycerol, and wherein the composition is a liquid, solid or gel
composition.
[0030] A composition of the present disclosure may be in solid or
liquid form. The composition may be a concentrate to be diluted,
rehydrated and/or dissolved in a solvent, including water, before
use. The composition may also be a ready-to-use (in-use)
composition. The composition may furthermore be an active cleaning
base ingredient to be incorporated into other cleaning or washing
compositions.
[0031] In one embodiment, the composition is adapted for delivery
to a washing machine to prevent fouling by bacterial species
capable of causing the laundry malodor "sweat". In another
embodiment, the composition is further adapted for delivery to a
washing machine by applications which include, but are not limited
to, solid, semi-solid, gel, liquid, aerosol, emulsion, and/or
powder applications alone and/or in combination with liquid, solid,
semisolid, aerosol, emulsion, and/or gel detergents, alone and/or
in combination with liquid, solid, semi-solid, aerosol, emulsion,
and/or gel fabric softeners, and/or alone and/or in combination
with any other laundry and/or washing maching additive.
[0032] In one aspect, the present disclosure provides a composition
adapted for application to a fabric. The composition adapted for
delivery to a fabric may be in the form of a solid, semi-solid,
gel, liquid, aerosol, emulsion, and/or powder, as a treatment for
fabrics to prevent fouling by bacterial species capable of causing
laundry malodor. In another embodiment, the composition is adapted
for delivery to a fabric by applications which include, but are not
limited to, solid, semi-solid, gel, liquid, aerosol, emulsion,
and/or powder applications alone and/or in combination with liquid,
solid, semi-solid, aerosol, emulsion, and/or gel detergents, alone
and/or in combination with liquid, solid, semi-solid, aerosol,
emulsion, and/or gel fabric softeners, and/or alone and/or in
combination with any other laundry and/or washing maching
additive.
[0033] When used in washing and cleaning agents for household
applications, such as detergents, fabric softeners, fabric
finishers, laundry performance enhancers, laundry care products,
automatic and hand dishwashing products, toilet care products, hard
surface cleaners such as cleaners for bathrooms, glass, floors and
kitchens, the composition can furthermore contain other usual
constituents of washing or cleaning agents, in particular textile
washing agents, selected in particular from the group of builders,
surfactants, polymers, enzymes, disintegration adjuvants, scents,
and perfume carriers.
[0034] Included among the builders are in particular zeolites,
silicates, carbonates, organic cobuilders, and--provided no
environmental prejudices against their use exist--also
phosphates.
[0035] The finely crystalline synthetic zeolite containing bound
water that is preferably used is zeolite A and/or zeolite P.
Zeolite MAP.RTM. (commercial product of the Crosfield Co.), for
example, is appropriate as zeolite P. Also suitable, however, are
zeolite X as well as mixtures of A, X, and/or P. Also commercially
available and usable in the context of the present disclosure is,
for example, a co-crystal of zeolite X and zeolite A (approx. 80 wt
% zeolite X) that can be described by the formula
nNa.sub.2O.(1-n)K.sub.2O.Al.sub.2O.sub.3.(2-2.5)SiO.sub.2.(3.5-5.5)H.sub-
.2O.
[0036] The zeolite can be used both as a builder in a granular
compound and as a kind of "dusting" on a granular mixture,
preferably a mixture to be compressed, both approaches to
incorporation of the zeolite into the pre-mixture usually being
used. Zeolites can exhibit an average particle size of less than
about 10 .mu.m (volume distribution; measurement method: Coulter
Counter), and preferably contain from about 18 wt % to about 22 wt
%, in particular from, about 20 wt % to about 22 wt %, bound
water.
[0037] Crystalline sheet silicates of the general formula
NaMSi.sub.xO.sub.2x+1.y H.sub.2O can also be used, where M
represents sodium or hydrogen, x is a number from about 1.9 to
about 22, preferably from about 1.9 to about 4, particularly
preferred values for x being 2, 3, or 4, and y denotes a number
from about 0 to about 33, preferably from about 0 to about 20. The
crystalline sheet silicates of the formula NaMSi.sub.xO.sub.2x+1.y
H.sub.2O are marketed, for example, by Clariant GmbH (Germany)
under the trade name Na-SKS. Examples of these silicates are
Na-SKS-1 (Na.sub.2Si.sub.22O.sub.45.x H.sub.2O, kenyaite), Na-SKS-2
(Na.sub.2Si.sub.14O.sub.29.x H.sub.2O, magadiite), Na-SKS-3
(Na.sub.2Si.sub.8O.sub.17.x H.sub.2O), or Na-SKS-4
(Na.sub.2Si.sub.4O.sub.9.x H.sub.2O, makatite).
[0038] Crystalline sheet silicates of the formula
NaMSi.sub.xO.sub.2x+1.y H.sub.2O in which x denotes 2 are
preferred. Both .beta.- and .delta.-sodium disilicates
Na.sub.2Si.sub.2O.sub.5.y H.sub.2O, as well as also principally
Na-SKS-5 (.alpha.-Na.sub.2Si.sub.2O.sub.5), Na-SKS-7
(.beta.-Na.sub.2Si.sub.2O.sub.5, natrosilite), Na-SKS-9
(NaHSi.sub.2O.sub.5.H.sub.2O), Na-SKS-10 (NaHSi.sub.2O.sub.5.3
H.sub.2O, kanemite), Na-SKS-11 (t-Na.sub.2Si.sub.2O.sub.5), and
Na-SKS-13 (NaHSi.sub.2O.sub.5), but in particular Na-SKS-6
(6-Na.sub.2Si.sub.2O.sub.5), are particularly preferred. Washing or
cleaning agents preferably contain a weight proportion of the
crystalline sheet silicates of the formula NaMSi.sub.xO.sub.2x+1.
yH.sub.2O from about 0.1 wt % to about 20 wt %, preferably from
about 0.2 wt % to about 15 wt %, and in particular from about 0.4
wt % to about 10 wt %.
[0039] Also usable are amorphous sodium silicates having a
Na.sub.2O:SiO.sub.2 modulus from about 1:2 to about 1:3.3,
preferably from about 1:2 to about 1:2.8, and in particular from
about 1:2 to about 1:2.6, which are preferably dissolution-delayed
and exhibit secondary washing properties. The dissolution delay as
compared with conventional amorphous sodium silicates can have been
brought about in various ways, for example by surface treatment,
compounding, compacting/densification, or overdrying. The term
"amorphous" is understood to mean that in X-ray diffraction
experiments the silicates do not yield the sharp X-ray reflections
that are typical of crystalline substances, but produce at most one
or more maxima in the scattered X radiation that have a width of
several degree units of the diffraction angle.
[0040] Alternatively or in combination with the aforesaid amorphous
sodium silicates, it is possible to use X-amorphous silicates whose
silicate particles yield blurred or even sharp diffraction maxima
in electron beam diffraction experiments. This is to be interpreted
to mean that the products comprise microcrystalline regions from
about 10 to several hundred nm in size, values of up to a maximum
of about 50 nm, and in particular up to a maximum of about 20 nm,
being preferred. X-amorphous silicates of this kind likewise
exhibit a dissolution delay as compared with conventional water
glasses. Densified/compacted amorphous silicates, compounded
amorphous silicates, and overdried X-amorphous silicates are
particularly preferred.
[0041] This/these silicate(s), preferably alkali silicates,
particularly preferably crystalline or amorphous alkali
disilicates, if present, are contained in washing and cleaning
agents in quantities from about 3 wt % to about 60 wt %, preferably
from about 8 wt % to about 50 wt %, and in particular from about 20
wt % to about 40 wt %.
[0042] Utilization of the commonly known phosphates as builder
substances is also possible, provided such use is not to be avoided
for environmental reasons. Among the plurality of commercially
obtainable phosphates, the alkali-metal phosphates have the
greatest significance in the washing- and cleaning-agent industry,
with particular preference for pentasodium resp. pentapotassium
triphosphate (sodium resp. potassium tripolyphosphate).
[0043] "Alkali-metal phosphates" is the summary designation for the
alkali-metal (in particular sodium and potassium) salts of the
various phosphoric acids, in which context a distinction can be
made between metaphosphoric acids (HPO.sub.3)n and orthophosphoric
acid H.sub.3PO.sub.4, in addition to higher-molecular-weight
representatives. The phosphates embody a combination of advantages:
they act as alkali carriers, prevent lime deposits on machine parts
resp. lime incrustations in fabrics, and furthermore contribute to
cleaning performance. Phosphates that are technically especially
important are pentasodium triphosphate Na.sub.5P.sub.3O.sub.10
(sodium tripolyphosphate) and the corresponding potassium salt
pentapotassium triphosphate K.sub.5P.sub.3O.sub.10 (potassium
tripolyphosphate). Sodium potassium tripolyphosphates are also used
with preference. If phosphates are employed in washing or cleaning
agents, preferred agents then contain that/those phosphate(s),
preferably alkali metal phosphate(s), particularly preferably
pentasodium resp. pentapotassium triphosphate (sodium resp.
potassium tripolyphosphate), in quantities from about 5 wt % to
about 80 wt %, preferably from about 15 wt % to about 75 wt %, and
in particular from about 20 wt % to about 70 wt %.
[0044] Alkali carriers are also usable. Alkali carriers are
considered to be, for example, alkali-metal hydroxides,
alkali-metal carbonates, alkali-metal hydrogen carbonates,
alkali-metal sesquicarbonates, the aforesaid alkali silicates,
alkali metasilicates, and mixtures of the aforesaid substances; the
alkali carbonates, in particular sodium carbonate, sodium hydrogen
carbonate, or sodium sesquicarbonate, are preferably used. A
builder system containing a mixture of tripolyphosphate and sodium
carbonate can be particularly preferred. Because of their low
chemical compatibility with the other ingredients of washing or
cleaning agents as compared with other builder substances, the
alkali-metal hydroxides are preferably used only in small
quantities, preferably in quantities below about 10 wt %,
preferably below about 6 wt %, particularly preferably below about
4 wt %, and in particular below about 2 wt %. Agents that contain,
based on their total weight, less than about 0.5 wt % and in
particular no alkali-metal hydroxides are particularly preferred.
It is preferred to use carbonate(s) and/or hydrogen carbonate(s),
preferably alkali carbonate(s), particularly preferably sodium
carbonate, in quantities from about 2 wt % to about 50 wt %,
preferably from about 5 wt % to about 40 wt %, and in particular
from about 7.5 wt % to about 30 wt %.
[0045] Organic builders that are to be recited are in particular
polycarboxylates/polycarboxylic acids, polymeric polycarboxylates,
aspartic acid, polyacetals, dextrins, as well as phosphonates.
Polycarboxylic acids are usable, for example, in the form of the
free acid and/or sodium salts thereof, "polycarboxylic acids" being
understood as those carboxylic acids which carry more than one acid
function. These are, for example, citric acid, adipic acid,
succinic acid, glutaric acid, malic acid, tartaric acid, maleic
acid, fumaric acid, sugar acids, aminocarboxylic acids,
nitrilotriacetic acid (NTA), provided such use is not objectionable
for environmental reasons, as well as mixtures thereof. The free
acids typically also possess, besides their builder effect, the
property of an acidifying component, and thus also serve to
establish a lower and milder pH for washing or cleaning agents. To
be recited in this context are, in particular, citric acid,
succinic acid, glutaric acid, adipic acid, gluconic acid, and any
mixtures thereof. Also suitable as builders are polymeric
polycarboxylates; these are, for example, the alkali metal salts of
polyacrylic acid or of polymethacrylic acid, for example those
having a relative molecular weight from about 500 to about 70,000
g/mol. Polyacrylates that preferably have a molecular weight from
about 2000 to about 20,000 g/mol are particularly suitable. Of this
group in turn, the short-chain polyacrylates, which have molar
masses from about 2000 to about 10,000 g/mol and particularly
preferably from about 3000 to about 5000 g/mol, can be preferred
because of their superior solubility. Also suitable are copolymeric
polycarboxylates, in particular those of acrylic acid with
methacrylic acid and of acrylic acid or methacrylic acid with
maleic acid. Copolymers of acrylic acid with maleic acid that
contain from about 50 wt % to about 90 wt % acrylic acid and from
about 50 wt % to about 10 wt % maleic acid have proven particularly
suitable. Their relative molecular weight, based on free acids, is
generally from about 2000 g/mol to about 70,000 g/mol, preferably
from about 20,000 g/mol to about 50,000 g/mol, and in particular
from about 30,000 gmol to about 40,000 g/mol. To improve water
solubility, the polymers can also contain allylsulfonic acids, for
example allyloxybenzenesulfonic acid and methallylsulfonic acid, as
monomers. The (co)polymeric polycarboxylates can be employed as a
solid or in aqueous solution. The concentration of (co)polymeric
polycarboxylates in washing or cleaning agents is preferably from
about 0.5 wt % to about 20 wt %, and in particular from about 3 wt
% to about 10 wt %.
[0046] Also particularly preferred are biodegradable polymers made
up of more than two different monomer units, for example those that
contain as monomers salts of acrylic acid and of maleic acid as
well as vinyl alcohol resp. vinyl alcohol derivatives, or that
contain as monomers salts of acrylic acid and of
2-alkylallylsulfonic acid, as well as sugar derivatives. Further
preferred copolymers are those that comprise acrolein and acrylic
acid/acrylic acid salts, resp. acrolein and vinyl acetate, as
monomers. Also to be mentioned as further preferred builder
substances are polymeric aminodicarboxylic acids, salts thereof, or
precursor substances thereof. Polyaspartic acids and/or salts
thereof are particularly preferred.
[0047] A further substance class having builder properties is
represented by phosphonates. These are the salts of, in particular,
hydroxyalkane- or aminoalkanephosphonic acids. Among the
hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonate
(HEDP) is of particular importance. It is employed in particular as
a sodium salt, the disodium salt reacting neutrally and the
tetrasodium salt in alkaline fashion. Suitable
aminoalkanephosphonic acids are, in particular,
ethylenediaminetetramethylenephosphonic acid (EDTMP),
diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their
higher homologs. They are used in particular in the form of the
neutrally reacting sodium salts, e.g. as the hexasodium salt of
EDTMP or as the hepta- and octasodium salt of DTPMP. Mixtures of
the aforesaid phosphonates can also be used as organic builders.
Aminoalkanephosphonates in particular moreover possess a pronounced
heavy-metal binding capability.
[0048] Further suitable builder substances are polyacetals, which
can be obtained by reacting dialdehydes with polyolcarboxylic acids
that comprise from about 5 to about 7 carbon atoms and at least
three hydroxyl groups. Preferred polyacetals are obtained from
dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and
mixtures thereof, and from polyolcarboxylic acids such as gluconic
acid and/or glucoheptonic acid.
[0049] Further suitable organic builder substances are dextrins,
for example oligomers resp. polymers of carbohydrates, which can be
obtained by partial hydrolysis of starches. Hydrolysis can be
carried out in accordance with usual, e.g. acid- or
enzyme-catalyzed, methods. These are preferably hydrolysis products
having average molar weights in the range from about 400 g/mol to
about 500,000 g/mol. A polysaccharide having a dextrose equivalent
(DE) in the range from about 0.5 to about 40, in particular from
about 2 to about 30, is preferred, DE being a common indicator of
the reducing effect of a polysaccharide as compared with dextrose,
which possesses a DE of about 100. Both maltodextrins having a DE
between from about 3 and about 20 and dry glucose syrups having a
DE between from about 20 and about 37, as well as so-called yellow
dextrins and white dextrins having higher molar weights in the
range from about 2000 to about 30,000 g/mol, are usable. The
oxidized derivatives of such dextrins are their reaction products
with oxidizing agents that are capable of oxidizing at least one
alcohol function of the saccharide ring to the carboxylic acid
function.
[0050] Oxydisuccinates and other derivatives of disuccinates,
preferably ethylenediamine disuccinate, are additional suitable
cobuilders. Ethylenediamine-N,N'-disuccinate (EDDS) is used here,
preferably in the form of its sodium or magnesium salts. Also
preferred in this context are glycerol disuccinates and glycerol
trisuccinates. If desired, suitable utilization quantities in
particular in zeolite-containing and/or silicate-containing
formulations are from about 3 wt % to about 15 wt %.
[0051] Other usable organic cobuilders are, for example, acetylated
hydroxycarboxylic acids resp. salts thereof, which can optionally
also be present in lactone form and which contain at least about 4
carbon atoms and at least one hydroxy group, as well as a maximum
of two acid groups.
[0052] All compounds that are capable of forming complexes with
alkaline earth ions can also be used as builders.
[0053] Washing and cleaning agents can contain nonionic, anionic,
cationic, and/or amphoteric surfactants.
[0054] All nonionic surfactants known to one skilled in the art can
be used as nonionic surfactants. With particular preference,
washing or cleaning agents contain nonionic surfactants from the
group of the alkoxylated alcohols. The nonionic surfactants used
are preferably alkoxylated, advantageously ethoxylated, in
particular primary alcohols having preferably from about 8 to about
18 carbon atoms and an average of from about 1 to about 12 mol
ethylene oxide (EO) per mol of alcohol, in which the alcohol
residue can be linear or preferably methyl-branched in the
2-position, resp. can contain mixed linear and methyl-branched
residues, such as those that are usually present in oxo alcohol
residues. Particularly preferred, however, are alcohol ethoxylates
having linear residues made up of alcohols of natural origin having
from about 12 to about 18 carbon atoms, e.g. from coconut, palm,
tallow, or oleyl alcohol, and an average of from about 2 to about 8
EO per mol of alcohol. The preferred ethoxylated alcohols include,
for example, C.sub.12-14 alcohols with 3 EO or 4 EO, C.sub.9-11
alcohols with 7 EO, C.sub.13-15 alcohols with 3 EO, 5 EO, 7 EO, or
8 EO, C.sub.12-18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures
thereof, such as mixtures of C.sub.12-14 alcohol with 3 EO and
C.sub.12-18 alcohol with 5 EO. The degrees of ethoxylation
indicated represent statistical averages that can correspond to an
integral or a fractional number for a specific product. Preferred
alcohol ethoxylates exhibit a restricted distribution of homologs
(narrow range ethoxylates, NRE).
[0055] Alternatively or in addition to these nonionic surfactants,
fatty alcohols with more than about 12 EO can also be used.
Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30
EO, or 40 EO. Also usable as further nonionic surfactants are
alkylglycosides of the general formula RO(G).sub.x in which R
corresponds to a primary straight-chain or methyl-branched
aliphatic residue, in particular methyl-branched in the 2-position,
having from about 8 to about 22, preferably from about 12 to about
18 carbon atoms, and G is the symbol that denotes a glycose unit
having 5 or 6 carbon atoms, preferably glucose. The degree of
oligomerization x, which indicates the distribution of
monoglycosides and oligoglycosides, is any number between about 1
and about 10; x is preferably from about 1.2 to about 1.4.
[0056] A further class of nonionic surfactants used in preferred
fashion, which are used either as the only nonionic surfactant or
in combination with other nonionic surfactants, are alkoxylated,
preferably ethoxylated or ethoxylated and propoxylated, fatty acid
alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl
chain.
[0057] Nonionic surfactants of the amine oxide type, for example
N-cocalkyl-N,N-dimethylamine oxide and
N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid
alkanolamides, can also be used. The quantity of these nonionic
surfactants is preferably equal to no more than that of the
ethoxylated fatty alcohols, in particular no more than half
thereof.
[0058] Further suitable surfactants are polyhydroxy fatty acid
amides of the formula
##STR00001##
in which R denotes an aliphatic acyl residue having from about 6 to
about 22 carbon atoms; R.sup.1 denotes hydrogen, an alkyl or
hydroxyalkyl residue having 1 to 4 carbon atoms; and [Z] denotes a
linear or branched polyhydroxyalkyl residue having from about 3 to
about 10 carbon atoms and from about 3 to about 10 hydroxyl groups.
Polyhydroxy fatty acid amides are known substances that can usually
be obtained by reductive amination of a reducing sugar with
ammonia, an alkylamine, or an alkanolamine, and subsequent
acylation with a fatty acid, a fatty acid alkyl ester, or a fatty
acid chloride. Also belonging to the group of the polyhydroxy fatty
acid amides are compounds of the formula
##STR00002##
in which R denotes a linear or branched alkyl or alkenyl residue
having from about 7 to about 12 carbon atoms; R.sup.1 denotes a
linear, branched, or cyclic alkyl residue or an aryl residue having
from about 2 to about 8 carbon atoms; and R.sup.2 denotes a linear,
branched, or cyclic alkyl residue or an aryl residue or an oxyalkyl
residue having from about 1 to about 8 carbon atoms, C.sub.1-4
alkyl or phenyl residues being preferred; and [Z] denotes a linear
polyhydroxyalkyl residue whose alkyl chain is substituted with at
least two hydroxyl groups, or alkoxylated, preferably ethoxylated
or propoxylated, derivatives of that residue. [Z] is preferably
obtained by reductive amination of a reduced sugar, for example
glucose, fructose, maltose, lactose, galactose, mannose, or xylose.
The N-alkoxy- or N-aryloxy-substituted compounds can be converted
into the desired polyhydroxy fatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as
catalyst.
[0059] Nonionic surfactants from the group of alkoxylated alcohols,
particularly preferably from the group of mixed alkoxylated
alcohols and in particular from the group of EO/AO/EO nonionic
surfactants or PO/AO/PO nonionic surfactants, especially PO/EO/PO
nonionic surfactants, are particularly preferred. These PO/EO/PO
nonionic surfactants are notable for good foam control.
[0060] Anionic surfactants used are, for example, those of the
sulfonate and sulfate types. Possibilities as surfactants of the
sulfonate type are, for example, preferably C.sub.9-13
alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene-
and hydroxyalkanesulfonates, and disulfonates, for example such as
those obtained from C.sub.12-18 monoolefins having a terminal or
internal double bond, by sulfonation with gaseous sulfur trioxide
and subsequent alkaline or acid hydrolysis of the sulfonation
products. Also suitable are alkanesulfonates that are obtained from
C.sub.12-18 alkanes, for example by sulfochlorination or
sulfoxidation with subsequent hydrolysis resp. neutralization. Also
suitable are the esters of .alpha.-sulfo fatty acids
(estersulfonates), for example the .alpha.-sulfonated methyl esters
of hydrogenated coconut, palm kernel, or tallow fatty acids.
[0061] Further suitable anionic surfactants are sulfonated fatty
acid glycerol esters. "Fatty acid glycerol esters" are to be
understood as the mono-, di- and triesters, and mixtures thereof,
that are obtained in the context of manufacture by esterification
of a monoglycerol with from about 1 to about 3 mol fatty acid, or
upon transesterification of triglycerides with from about 0.3 to
about 2 mol glycerol. Preferred sulfonated fatty acid glycerol
esters are the sulfonation products of saturated fatty acids having
from about 6 to about 22 carbon atoms, for example hexanoic acid,
octanoic acid, decanoic acid, myristic acid, lauric acid, palmitic
acid, stearic acid, or behenic acid.
[0062] Preferred alk(en)yl sulfates are the alkali, and in
particular sodium salts of the sulfuric acid semi-esters of
C.sub.12-18 fatty alcohols, for example from coconut fatty alcohol,
tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol,
or C.sub.10 to C.sub.20 oxo alcohols, and those semi-esters of
secondary alcohols of those chain lengths. Also preferred are
alk(en)yl sulfates of the aforesaid chain length that contain a
synthetic straight-chain alkyl residue produced on a petrochemical
basis, which possess a breakdown behavior analogous to those
appropriate compounds based on fat-chemistry raw materials. For
purposes of washing technology, the C.sub.12 to C.sub.16 alkyl
sulfates and C.sub.12 to C.sub.15 alkyl sulfates, as well as
C.sub.14 to C.sub.15 alkyl sulfates, are preferred. 2,3-Alkyl
sulfates that can be obtained, for example, as commercial products
of the Shell Oil Company under the name DAN.RTM., are also suitable
anionic surfactants.
[0063] Sulfuric acid monoesters of straight-chain or branched
C.sub.7-21 alcohols ethoxylated with from about 1 to about 6 mol
ethylene oxide, such as 2-methyl-branched C.sub.9-11 alcohols with
an average of 3.5 mol ethylene oxide (EO) or C.sub.12-18 fatty
alcohols with from about 1 to about 4 EO, are also suitable.
Because of their high-foaming behavior they are used in cleaning
agents only in relatively small quantities, for example in
quantities from about 1 wt % to about 5 wt %.
[0064] Other suitable anionic surfactants are also the salts of
alkylsulfosuccinic acid, which are also referred to as
sulfosuccinates or as sulfosuccinic acid esters and represent the
monoesters and/or diesters of sulfosuccinic acid with alcohols,
preferably fatty alcohols, and in particular ethoxylated fatty
alcohols. Preferred sulfosuccinates contain C.sub.8-18 fatty
alcohol residues or mixtures thereof. Particularly preferred
sulfosuccinates contain a fatty alcohol residue that derives from
ethoxylated fatty alcohols that, considered per se, represent
nonionic surfactants. Sulfosuccinates whose fatty alcohol residues
derive from ethoxylated fatty alcohols having a restricted homolog
distribution are, in turn, particularly preferred. It is likewise
also possible to use alk(en)ylsuccinic acid having preferably from
about 8 to about 18 carbon atoms in the alk(en)yl chain, or salts
thereof.
[0065] Soaps are particularly appropriate as further anionic
surfactants. Saturated fatty acid soaps, such as salts of lauric
acid, myristic acid, palmitic acid, stearic acid, hydrogenated
erucic acid and behenic acid, are suitable, as are soap mixtures
derived in particular from natural fatty acids, e.g. coconut,
palm-kernel, or tallow fatty acids.
[0066] The anionic surfactants, including soaps, can be present in
the form of their sodium, potassium, or ammonium salts and as
soluble salts of organic bases such as mono-, di-, or
triethanolamine. The anionic surfactants are preferably present in
the form of their sodium or potassium salts, in particular in the
form of sodium salts.
[0067] Instead of or in combination with the aforesaid surfactants,
cationic and/or amphoteric surfactants can also be used.
[0068] Cationic active substances that can be used are, for
example, cationic compounds of the following formulas:
##STR00003##
in which each group R.sup.1 is selected mutually independently from
C.sub.1-6 alkyl, alkenyl, or hydroxyalkyl groups; each group
R.sup.2 is selected mutually independently from C.sub.8-28 alkyl or
alkenyl groups; R.sup.3=R.sup.1 or (CH.sub.2).sub.n-T-R.sup.2;
R.sup.4=R.sup.1 or R.sup.2 or (CH.sub.2).sub.n-T-R.sup.2;
T=--CH.sub.2--, --O--CO--, or --CO--O--, and n is an integer from 0
to 5.
[0069] Textile-softening compounds can be used for textile care and
in order to improve textile properties, such as a softer "hand"
(avivage) and decreased electrostatic charge (increased wearing
comfort). The active agents in these formulations are quaternary
ammonium compounds having two hydrophobic residues, for example
distearyldimethylammonium chloride, although because of its
insufficient biodegradability the latter is increasingly being
replaced by quaternary ammonium compounds that contain ester groups
in their hydrophobic residues as defined break points for
biodegradation.
[0070] "Esterquats" of this kind having improved biodegradability
are obtainable, for example, by esterifying mixtures of methyl
diethanolamine and/or triethanolamine with fatty acids and then
quaternizing the reaction products in known fashion with alkylating
agents. Dimethylolethylene urea is additionally suitable as a
finish.
[0071] Enzymes can be used to increase the performance of washing
or cleaning agents. These include in particular proteases,
amylases, lipases, hemicellulases, cellulases, perhydrolases, or
oxidoreductases, as well as preferably mixtures thereof. These
enzymes are in principle of natural origin; proceeding from the
natural molecules, improved variants are available for use in
washing or cleaning agents and are used in correspondingly
preferred fashion. Washing or cleaning agents contain enzymes
preferably in total quantities from about 1.times.10.sup.-6 to
about 5 wt %, based on active protein. The protein concentration
can be determined with the aid of known methods, for example the
BCA method or the biuret method.
[0072] Among the proteases, those of the subtilisin type are
preferred. Examples thereof are subtilisins BPN' and Carlsberg and
further developed forms thereof, protease PB92, subtilisins 147 and
309, the alkaline protease from Bacillus lentus, subtilisin DY, and
the enzymes (to be classified, however, as subtilases and no longer
as subtilisins in the strict sense) thermitase, proteinase K, and
proteases TW3 and TW7.
[0073] Examples of usable amylases are the .alpha.-amylases from
Bacillus licheniformis, from B. amyloliquefaciens, from B.
stearothermophilus, from Aspergillus niger and A. oryzae, and the
further developments of the aforementioned amylases improved for
use in washing and cleaning agents. Additionally to be highlighted
for this purpose are the .alpha.-amylase from Bacillus sp. A 7-7
(DSM 12368) and the cyclodextrin-glucanotransferase (CGTase) from
B. agaradherens (DSM 9948).
[0074] Lipases or cutinases are usable because of their
triglyceride-cleaving activity. Included thereamong are, for
example, the lipases obtainable originally from Humicola lanuginosa
(Thermomyces lanuginosus) or lipases further developed therefrom,
in particular those having the D96L amino acid exchange. Also
usable, for example, are the cutinases that were originally
isolated from Fusarium solani pisi and Humicola insolens. Lipases
and/or cutinases whose starting enzymes were originally isolated
from Pseudomonas mendocina and Fusarium solanii are furthermore
usable.
[0075] Enzymes that are grouped under the term "hemicellulases" can
also be used. These include, for example, mannanases,
xanthanlyases, pectinlyases (=pectinases), pectinesterases,
pectatelyases, xyloglucanases (=xylanases), pullulanases, and
.beta.-glucanases.
[0076] Oxidoreductases, for example oxidases, oxygenases,
catalases, peroxidases such as halo-, chloro-, bromo-, lignin,
glucose, or manganese peroxidases, dioxygenases, or laccases
(phenoloxidases, polyphenoloxidases), can be used if desired to
intensify the bleaching effect. Advantageously, preferably organic,
particularly preferably aromatic compounds that interact with the
enzymes are additionally added in order to enhance the activity of
the relevant oxidoreductases (enhancers) or, if there is a large
difference in redox potential between the oxidizing enzymes and the
stains, to ensure electron flow (mediators).
[0077] Enzymes can be used in any form established according to the
existing art. This includes, for example, the solid preparations
obtained by granulation, extrusion, or lyophilization or, in
particular in the case of liquid or gelled agents, solutions of the
enzymes, advantageously as concentrated as possible, low in water
and/or with added stabilizers. Alternatively, the enzymes can be
encapsulated for both the solid and the liquid administration form,
for example by spray drying or extrusion of the enzyme solution
together with a preferably natural polymer, or in the form of
capsules, for example those in which the enzymes are enclosed e.g.
in a solidified gel, or in those of the core-shell type, in which
an enzyme-containing core is coated with a water-, air-, and/or
chemical-impermeable protective layer. Further active agents, for
example stabilizers, emulsifiers, pigments, bleaches, or dyes, can
additionally be applied in superimposed layers. Such capsules are
applied using methods known per se, for example by vibratory or
roll granulation or in fluidized bed processes. Advantageously,
such granulates are low in dust, for example as a result of the
application of polymeric film-formers, and are shelf-stable because
of the coating. It is furthermore possible to package two or more
enzymes together, so that a single granulate exhibits multiple
enzyme activities.
[0078] One or more enzymes and/or enzyme preparations, preferably
protease preparations and/or amylase preparations, are preferably
used, in quantities from about 0.1 wt % to about 5 wt %, preferably
from about 0.2 wt % to about 4.5 wt %, and in particular from about
0.4 wt % to about 4 wt %.
[0079] Individual fragrance compounds, e.g. synthetic products of
the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon types,
can be used as perfume oils resp. scents. It is preferred, however,
to use mixtures of different fragrances that together generate an
attractive scent note. Such perfume oils can also contain natural
fragrance mixtures such as those accessible from plant sources, for
example pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil.
In order to be perceptible, a fragrance must be volatile; in
addition to the nature of the functional groups and the structure
of the chemical compound, the molecular weight also plays an
important part. Most fragrances, for example, possess molar weights
of up to approximately 200 g/mol, while molar weights of about 300
g/mol and above represent something of an exception. Because of the
differing volatility of fragrances, the odor of a perfume or
fragrance made up of multiple fragrances changes during
volatilization, the odor impressions being subdivided into a "top
note," "middle note" or "body," and "end note" or "dry out."
Because the perception of an odor also depends a great deal on the
odor intensity, the top note of a perfume or scent is not made up
only of highly volatile compounds, while the end note comprises for
the most part less-volatile, i.e. adherent fragrances. In the
compounding of perfumes, more-volatile fragrances can, for example,
be bound to specific fixatives, thereby preventing them from
volatilizing too quickly. The division below of fragrances into
"more-volatile" and "adherent" fragrances therefore makes no
statement with regard to the odor impression, or as to whether the
corresponding fragrance is perceived as a top or middle note. The
scents can be processed directly, but it can also be advantageous
to apply the scents onto carriers that ensure a slower scent
release for a lasting scent. Cyclodextrins, for example, have
proven successful as such carrier materials; the
cyclodextrin-perfume complexes can additionally be coated with
further adjuvants.
[0080] In selecting the coloring agent, care must be taken that the
coloring agents exhibit excellent shelf stability and insensitivity
to light, and they cannot have too strong an affinity with respect
to textile surfaces and, particularly in this case, toward
synthetic fibers. At the same time, it must also be considered that
coloring agents have differing levels of stability with respect to
oxidation. It is generally the case that water-insoluble coloring
agents are more stable with respect to oxidation than water-soluble
coloring agents. The concentration of the coloring agent in the
washing or cleaning agents varies as a function of solubility and
thus also of oxidation sensitivity. For readily water-soluble
coloring agents, coloring-agent concentrations in the range of from
about 10.sup.-2 wt % to about 10.sup.-2 wt % are typically
selected. In the case of pigment dyes, on the other hand, which are
particularly preferred because of their brilliance but are less
readily water-soluble, the appropriate concentration of the
coloring agent in washing or cleaning agents is typically from
about 10.sup.-3 wt % to about 10.sup.-4 wt %. Coloring agents that
can be oxidatively destroyed in a washing process, as well as
mixtures thereof with suitable blue dyes, so-called bluing agents,
are preferred. It has proven advantageous to use coloring agents
that are soluble in water or at room temperature in liquid organic
substances. Anionic coloring agents, e.g. anionic nitroso dyes, are
suitable, for example.
[0081] In addition to the components recited hitherto, the washing
or cleaning agents can contain further ingredients that further
improve the applications-engineering and/or aesthetic properties of
said agents. Preferred agents contain one or more substances from
the group of electrolytes, pH adjusting agents, fluorescing agents,
hydrotopes, foam inhibitors, silicone oils, anti-redeposition
agents, optical brighteners, anti-gray agents, shrinkage
preventers, crease prevention agents, color transfer inhibitors,
antimicrobial active agents, germicides, fungicides, antioxidants,
antistatic agents, ironing adjuvants, proofing and impregnation
agents, swelling and anti-slip agents, and UV absorbers.
[0082] A large number of very varied salts from the group of the
inorganic salts can be used as electrolytes. Preferred cations are
the alkali and alkaline-earth metals; preferred anions are the
halides and sulfates. From a production-engineering standpoint, the
use of NaCl or MgCl.sub.2 in the washing or cleaning agents is
preferred.
[0083] In order to bring the pH of washing or cleaning agents into
the desired range, the use of pH adjusting agents may be indicated.
All known acids resp. bases are usable here, provided their use is
not prohibited for environmental or applications-engineering
reasons, resp. for reasons of consumer safety. The quantity of
these adjusting agents usually does not exceed 1 wt % of the total
formulation.
[0084] Appropriate foam inhibitors are soaps, oils, fats,
paraffins, or silicone oils, which optionally can be applied onto
carrier materials. Suitable carrier materials are, for example,
inorganic salts such as carbonates or sulfates, cellulose
derivatives, or silicates, as well as mixtures of the aforesaid
materials. Agents preferred in the context of the present
application contain paraffins, preferably unbranched paraffins
(n-paraffins), and/or silicones, preferably linear-polymer
silicones, which are constructed according to the
(R.sub.2SiO).sub.x pattern and are also referred to as silicone
oils. These silicone oils usually represent clear, colorless,
neutral, odorless, hydrophobic liquids having a molecular weight
between from about 1000 g/mol and about 150,000 g/mol and
viscosities between about 10 mPas and about 1,000,000 mPas.
[0085] Suitable anti-redeposition agents are, for example, nonionic
cellulose ethers such as methyl cellulose and methylhydroxypropyl
cellulose having a from about 15 to about 30 wt % proportion of
methoxy groups and a from about 1 to about 15 wt % proportion of
hydroxypropyl groups, based in each case on the nonionic cellulose
ether.
[0086] Suitable soil repellents are polymers, known from the
existing art, of phthalic acid and/or terephthalic acid resp.
derivatives thereof, in particular polymers of ethylene
terephthalate and/or polyethylene glycol terephthalate or
anionically and/or nonionically modified derivatives thereof. Of
these, the sulfonated derivatives of phthalic acid polymers and
terephthalic acid polymers are particularly preferred.
[0087] Optical brighteners can be added in particular to washing
agents in order to eliminate graying and yellowing of the treated
textiles. These substances absorb onto the fibers and cause
brightening and a simulated bleaching effect by converting
invisible ultraviolet radiation into longer-wave visible light, the
ultraviolet light absorbed from sunlight being emitted as slightly
bluish fluorescence and resulting, with the yellow tone of the
grayed or yellowed laundry, in pure white. Suitable compounds
derive, for example, from the substance classes of
4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids),
4,4'-distyrylbiphenyls, methylumbelliferones, cumarins,
dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides,
benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene
derivatives substituted with heterocycles.
[0088] The purpose of anti-gray agents is to keep dirt that has
been detached from fibers suspended in the bath, and thus to
prevent redeposition of the dirt. Water-soluble colloids, usually
organic in nature, are suitable for this, for example water-soluble
salts of polymeric carboxylic acids, size, gelatin, salts of
ethersulfonic acids of starch or of cellulose, or salts of acidic
sulfuric-acid esters of cellulose or of starch. Water-soluble
polyamides containing acid groups are also suitable for this
purpose. Soluble starch preparations can furthermore be used, for
example degraded starch, aldehyde starches, etc.
Polyvinylpyrrolidone is also usable. Cellulose ethers such as
carboxymethyl cellulose (sodium salt), methyl cellulose,
hydroxyalkyl cellulose, and mixed ethers such as methylhydroxyethyl
cellulose, methylhydroxypropyl cellulose, methylcarboxymethyl
cellulose, and mixtures thereof, are also usable as anti-gray
agents.
[0089] Because textile fabrics, in particular those made of rayon,
viscose, cotton, and mixtures thereof, can tend to wrinkle because
the individual fibers are sensitive to bending, kinking,
compression, and squeezing perpendicularly to the fiber direction,
synthetic crease-prevention agents can be used. These include, for
example, synthetic products based on fatty acids, fatty acid
esters, fatty acid amides, fatty acid alkylol esters, fatty acid
alkylolamides, or fatty alcohols that are usually reacted with
ethylene oxide, or products based on lecithin or modified
phosphoric acid esters.
[0090] The purpose of proofing and impregnation methods is to
finish textiles with substances that prevent the deposition of dirt
or make it easier to wash out. Preferred proofing and impregnation
agents are perfluorinated fatty acids, including in the form of
their aluminum and zirconium salts, organic silicates, silicones,
polyacrylic acid esters having perfluorinated alcohol components,
or polymerizable compounds coupled to a perfluorinated acyl or
sulfonyl residue. Antistatic agents can also be contained.
Dirt-repellent finishing with proofing and impregnation agents is
often categorized as an "easy-care" finish. Penetration of the
impregnation agents, in the form of solutions or emulsions of the
relevant active agents, can be facilitated by the addition of
wetting agents that reduce surface tension. A further area of use
of proofing and impregnation agents is water-repellent finishing of
textile materials, tents, awnings, leather, etc. in which, in
contrast to waterproofing, the fabric pores are not sealed, i.e.
the material is still able to "breathe" (hydrophobizing). The
hydrophobizing agents used for hydrophobizing cover the textiles,
leather, paper, wood, etc. with a very thin layer of hydrophobic
groups such as longer alkyl chains or siloxane groups. Suitable
hydrophobizing agents are, for example, paraffins, waxes, metal
soaps, etc. having added portions of aluminum or zirconium salts,
quaternary ammonium compounds with long-chain alkyl residues, urea
derivatives, fatty acid-modified melamine resins, chromium-complex
salts, silicones, organo-tin compounds, and glutaric dialdehyde, as
well as perfluorinated compounds. The hydrophobized materials are
not oily to the touch, but water droplets bead up on them
(similarly to oiled fabrics) without wetting them.
Silicone-impregnated textiles, for example, have a soft hand and
are water- and dirt-repellent; drops of ink, wine, fruit juice, and
the like are easier to remove.
[0091] Antimicrobial active substances can be used in order to
counteract microorganisms, if they do not inhibit the function of
the bacterial spores of the present disclosure. A distinction is
made here, in terms of the antimicrobial spectrum and mechanism of
action, between bacteriostatics and bactericides, fungistatics and
fungicides, etc. Substances from these groups are, for example,
benzalkonium chlorides, alkylarylsulfonates, halogen phenols, and
phenol mercuric acetate; these compounds can also be entirely
omitted.
[0092] The agents can contain antioxidants in order to prevent
undesirable changes to the washing and cleaning agents and/or to
the treated textiles caused by the action of oxygen and other
oxidative processes. This class of compounds includes, for example,
substituted phenols, hydroquinones, catechols, and aromatic amines,
as well as organic sulfides, polysulfides, dithiocarbamates,
phosphites, and phosphonates.
[0093] Increased wearing comfort can result from the additional use
of antistatic agents. Antistatic agents increase the surface
conductivity and thus make possible improved dissipation of charges
that have formed. External antistatic agents are usually substances
having at least one hydrophilic molecule ligand, and yield a more
or less hygroscopic film on the surfaces. These usually
surface-active antistatic agents can be subdivided into
nitrogen-containing (amines, amides, quaternary ammonium
compounds), phosphorus-containing (phosphoric acid esters), and
sulfur-containing antistatic agents (alkylsulfonates, alkyl
sulfates). Lauryl-(resp. stearyl)dimethylbenzylammonium chlorides
are likewise suitable as antistatic agents for textile fabrics
resp. as an additive to washing agents, an avivage effect
additionally being achieved.
[0094] Silicone derivatives can be used in textile washing agents
in order to improve the water absorption capability and
rewettability of the treated textile fabrics and to facilitate
ironing of the treated textiles. These additionally improve the
rinsing behavior of washing or cleaning agents thanks to their
foam-inhibiting properties. Preferred silicone derivatives are, for
example, polydialkyl- or alkylarylsiloxanes in which the alkyl
groups comprise one to five carbon atoms and are entirely or partly
fluorinated. Preferred silicones are polydimethylsiloxanes, which
optionally can be derivatized and are then aminofunctional or
quaternized resp. comprise Si--OH, Si--H, and/or Si--Cl bonds.
Further preferred silicones are the polyalkylene oxide-modified
polysiloxanes, i.e. polysiloxanes that comprise, for example,
polyethylene glycols, as well as polyalkylene oxide-modified
dimethylpolysiloxanes.
[0095] Lastly, UV absorbers, which are absorbed onto the treated
textiles and improve the light-fastness of the fibers, can also be
used. Compounds that exhibit these desired properties are, for
example, the compounds that act by radiationless deactivation, and
derivatives of benzophenone having substituents in the 2- and/or
4-position. Also suitable are substituted benzotriazoles, acrylates
phenyl-substituted in the 3-position (cinnamic acid derivatives)
optionally having cyano groups in the 2-position, salicylates,
organic nickel complexes, and natural substances such as
umbelliferone and endogenous urocanic acid.
[0096] Protein hydrolysates are further suitable active substances
because of their fiber-care-providing effect. Protein hydrolysates
are product mixtures that are obtained by acid-, base-, or
enzyme-catalyzed breakdown of proteins. Protein hydrolysates of
both vegetable and animal origin can be used. Animal protein
hydrolysates are, for example, elastin, collagen, keratin, silk,
and milk protein hydrolysates, which can also be present in the
form of salts. It is preferred to use protein hydrolysates of
vegetable origin, e.g. soy, almond, rice, pea, potato, and wheat
protein hydrolysates. Although the use of protein hydrolysates as
such is preferred, amino acid mixtures obtained in other ways, or
individual amino acids such as arginine, lysine, histidine, or
pyroglutamic acid, can also optionally be used instead of them. It
is also possible to employ derivatives of protein hydrolysates, for
example in the form of their fatty acid condensation products.
EXAMPLES
Example 1: Prevention of Odor in Test Tubes
[0097] In test tubes, sterile human sweat was fermented with
various microorganisms, known to produce the malodor "sweat".
Bacterial spores of Bacillus tequilensis were added and the mixture
incubated for up to 27 hours.
[0098] Persons trained in olfaction smelled the tubes and rated the
intensity of the malodor on a scale of 0 to 4 (0 being no odor,
1=weak odor, 2=moderate odor, 3=strong odor, 4=extremely strong
odor).
[0099] The results are presented in Table 1:
TABLE-US-00001 TABLE 1 Malodor scores With spores, Incubation time
Control Bacillus tequilensis, [hours] (without spores) dosage 2.5
.times. 10.sup.2 cfu/ml 19 1.7 1.0 27 2.5 2.3
[0100] The results show the significantly improved performance of
the use of bacterial spores for the elimination of the malodor
"sweat".
[0101] While at least one exemplary embodiment has been presented
in the foregoing detailed description of the present disclosure, it
should be appreciated that a vast number of variations exist. It
should also be appreciated that the exemplary embodiment or
exemplary embodiments are only examples, and are not intended to
limit the scope, applicability, or configuration of the present
disclosure in any way. Rather, the foregoing detailed description
will provide those skilled in the art with a convenient road map
for implementing an exemplary embodiment of the present disclosure,
it being understood that various changes may be made in the
function and arrangement of elements described in an exemplary
embodiment without departing from the scope of the present
disclosure as set forth in the appended claims and their legal
equivalents.
* * * * *